Remotely-excited fluorine and water vapor etch

ABSTRACT

A method of etching exposed silicon oxide on patterned heterogeneous structures is described and includes a remote plasma etch formed from a fluorine-containing precursor. Plasma effluents from the remote plasma are flowed into a substrate processing region where the plasma effluents combine with water vapor. The chemical reaction resulting from the combination produces reactants which etch the patterned heterogeneous structures to produce, in embodiments, a thin residual structure exhibiting little deformation. The methods may be used to conformally trim silicon oxide while removing little or no silicon, polysilicon, silicon nitride, titanium or titanium nitride. In an exemplary embodiment, the etch processes described herein have been found to remove mold oxide around a thin cylindrical conducting structure without causing the cylindrical structure to significantly deform.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application claims the benefit of U.S. Prov. Pat. App. No. 61/445,295 filed Feb. 22, 2011, and titled “REMOTELY-EXCITED-FLUORINE AND WATER ETCH,” which is incorporated herein by reference for all purposes.

BACKGROUND OF THE INVENTION

Integrated circuits are made possible by processes which produce intricately patterned material layers on substrate surfaces. Producing patterned material on a substrate requires controlled methods for removal of exposed material. Chemical etching is used for a variety of purposes including transferring a pattern in photoresist into underlying layers, thinning layers or thinning lateral dimensions of features already present on the surface. Often it is desirable to have an etch process which etches one material faster than another helping e.g. a pattern transfer process proceed. Such an etch process is said to be selective to the first material. As a result of the diversity of materials, circuits and processes, etch processes have been developed with a selectivity towards a variety of materials.

A wet HF etch preferentially removes silicon oxide over other dielectrics and semiconductors. However, wet processes are unable to penetrate some constrained trenches and sometimes deform the remaining material. Dry etches produced in local plasmas (plasmas within the substrate processing region) can penetrate more constrained trenches and exhibit less deformation of delicate remaining structures. However, local plasmas can damage the substrate through the production of electric arcs as they discharge.

A Siconi™ etch is a remote plasma assisted dry etch process which involves the simultaneous exposure of a substrate to H₂, NF₃ and NH₃ plasma by-products. Remote plasma excitation of the hydrogen and fluorine species allows plasma-damage-free substrate processing. The Siconi™ etch is largely conformal and selective towards silicon oxide layers but does not readily etch silicon regardless of whether the silicon is amorphous, crystalline or polycrystalline. Silicon nitride is typically etched at a rate between silicon and silicon oxide, but the selectivity of silicon oxide over silicon nitride is typically not as pronounced as the selectivity of silicon oxide over silicon. The selectivity provides advantages for applications such as shallow trench isolation (STI) and inter-layer dielectric (ILD) recess formation. The Siconi™ process produces solid by-products which grow on the surface of the substrate as substrate material is removed. The solid by-products are subsequently removed via sublimation when the temperature of the substrate is raised. As a consequence of the production of solid by-products, Siconi™ etch process can deform delicate remaining structures as well.

Methods are needed to selectively remove silicon oxide while not disturbing delicate structures on a patterned substrate.

BRIEF SUMMARY OF THE INVENTION

A method of etching exposed silicon oxide on patterned heterogeneous structures is described and includes a remote plasma etch formed from a fluorine-containing precursor. Plasma effluents from the remote plasma are flowed into a substrate processing region where the plasma effluents combine with water vapor. The chemical reaction resulting from the combination produces reactants which etch the patterned heterogeneous structures to produce, in embodiments, a thin residual structure exhibiting little deformation. The methods may be used to conformally trim silicon oxide while removing little or no silicon, polysilicon, silicon nitride, titanium or titanium nitride. In an exemplary embodiment, the etch processes described herein have been found to remove mold oxide around a thin cylindrical conducting structure without causing the cylindrical structure to significantly deform.

Embodiments of the invention include methods of etching a patterned substrate in a substrate processing region of a substrate processing chamber. The patterned substrate has an exposed silicon oxide region. The methods include flowing a fluorine-containing precursor into a remote plasma region fluidly coupled to the substrate processing region while forming a remote plasma in the remote plasma region to produce plasma effluents. The methods further include flowing water vapor into the substrate processing region without first passing the water vapor through the remote plasma region. The methods further include etching the exposed silicon oxide region by flowing the plasma effluents into the substrate processing region.

Additional embodiments and features are set forth in part in the description that follows, and in part will become apparent to those skilled in the art upon examination of the specification or may be learned by the practice of the disclosed embodiments. The features and advantages of the disclosed embodiments may be realized and attained by means of the instrumentalities, combinations, and methods described in the specification.

BRIEF DESCRIPTION OF THE DRAWINGS

A further understanding of the nature and advantages of the disclosed embodiments may be realized by reference to the remaining portions of the specification and the drawings.

FIG. 1 is a flow chart of a silicon oxide selective etch process according to disclosed embodiments.

FIGS. 2A-2B are charts of etch rate dependence on substrate temperature and chamber pressure for silicon oxide selective etch processes according to disclosed embodiments.

FIG. 3 is a chart of silicon oxide selectivity compared to silicon nitride and silicon for silicon oxide selective etch processes according to disclosed embodiments.

FIG. 4A shows a substrate processing chamber according to embodiments of the invention.

FIG. 4B shows a showerhead of a substrate processing chamber according to embodiments of the invention.

FIG. 5 shows a substrate processing system according to embodiments of the invention.

In the appended figures, similar components and/or features may have the same reference label. Further, various components of the same type may be distinguished by following the reference label by a dash and a second label that distinguishes among the similar components. If only the first reference label is used in the specification, the description is applicable to any one of the similar components having the same first reference label irrespective of the second reference label.

DETAILED DESCRIPTION OF THE INVENTION

A method of etching exposed silicon oxide on patterned heterogeneous structures is described and includes a remote plasma etch formed from a fluorine-containing precursor. Plasma effluents from the remote plasma are flowed into a substrate processing region where the plasma effluents combine with water vapor. The chemical reaction resulting from the combination produces reactants which etch the patterned heterogeneous structures to produce, in embodiments, a thin residual structure exhibiting little deformation. The methods may be used to conformally trim silicon oxide while removing little or no silicon, polysilicon, silicon nitride, titanium or titanium nitride. In an exemplary embodiment, the etch processes described herein have been found to remove mold oxide around a thin cylindrical conducting structure without causing the cylindrical structure to significantly deform.

Selective remote gas phase etch processes have used a hydrogen source of ammonia (NH₃) and a fluorine source of nitrogen trifluoride (NF₃) which together flow through a remote plasma system (RPS) and into a reaction region. The flow rates of ammonia and nitrogen trifluoride are typically chosen such that the atomic flow rate of hydrogen is roughly twice that of fluorine in order to efficiently utilize the constituents of the two process gases. The presence of hydrogen and fluorine allows the formation of solid byproducts of (NH₄)₂SiF₆ at relatively low substrate temperatures. The solid byproducts are removed by raising the temperature of the substrate above the sublimation temperature. Remote gas phase etch processes remove oxide films much more rapidly than, e.g. silicon. However, the selectivity of traditional selective remote gas phase etch processes compared to silicon nitride may be poor. The inventors have discovered that the selectivity of silicon oxide over silicon nitride can be enhanced by exciting a fluorine-containing precursor in a remote plasma and combining the plasma effluents with water vapor which has not passed through a remote plasma system.

In order to better understand and appreciate the invention, reference is now made to FIG. 1 which is a flow chart of a silicon oxide selective etch process 100 according to disclosed embodiments. Prior to the first operation, a gap is formed in a patterned substrate. The gap is filled with a mold silicon oxide used to guide the deposition of a titanium nitride column. The titanium nitride column is formed near the center of the gap and is surrounded by the mold silicon oxide. Both the silicon oxide and the titanium nitride have exposed regions, in embodiments, prior to delivering the substrate into a processing region (operation 110).

A flow of nitrogen trifluoride is initiated into a plasma region separate from the processing region (operation 120). Other sources of fluorine may be used to augment or replace the nitrogen trifluoride. In general, a fluorine-containing precursor is flowed into the plasma region and the fluorine-containing precursor comprises at least one precursor selected from the group consisting of atomic fluorine, diatomic fluorine, nitrogen trifluoride, carbon tetrafluoride, hydrogen fluoride and xenon &fluoride. The separate plasma region may be referred to as a remote plasma region herein and may be within a distinct module from the processing chamber or a compartment within the processing chamber. The plasma effluents formed in the remote plasma region are then flowed into the substrate processing region (operation 125). At this point, the gas phase etch would have little selectivity towards silicon oxide and would have limited utility. However, water vapor is simultaneously flowed into the substrate processing region (operation 130) to react with the plasma effluents. The water vapor is not passed through the remote plasma region and therefore is only excited by interaction with the plasma effluents.

The patterned substrate is selectively etched (operation 135) such that the mold silicon oxide is removed from around the titanium nitride column. The removed material around the titanium nitride column forms a continuous trench in the shape of a moat. The reactive chemical species are removed from the substrate processing region and then the substrate is removed from the processing region (operation 145).

An architecture of dynamic random access memory (DRAM) is based on a cylindrical conductor, e.g. the titanium nitride column in the exemplary process flow. This architecture has been referred to as a one cylindrical storage node (OCS). The conducting cylinder may have a diameter less than 70 nm, less than 50 nm or less than 40 nm in different embodiments. Especially for small diameter conducting cylinders, the shape may significantly deviate from that of a cylinder. The conducting column may be cylindrical, square, rectangular, hexagonal or octagonal, in addition to a myriad of other shapes. The conducting column may comprise a variety of electrically conducting materials such as titanium, titanium nitride, polysilicon, tungsten, copper and the like. DRAM's are based on capacitive storage and benefit from larger capacitance per storage cell. The capacitance is controlled by selection of the surface area of the cylinder (i.e. the column) but also the separation of the column from the opposing electrode which would be deposited later (e.g. via a dielectric then metal deposition sequence). The conducting columns like the titanium nitride in the example need to remain substantially vertical after the mold silicon oxide is removed. The selective silicon oxide etches presented herein are especially suited to accomplish this type of task.

Wet etches have been used to remove the mold oxide but have been found to result in conducting columns which lean toward one another. A variety of other deviations from the shape of the pre-etch conducting column are possible and will be referred to generally as bowing. For example, the center of the conducting column may bow out while the tip and base remain relatively close to the pre-etch position. All deformations can inhibit the ability to further deposit a thin dielectric layer and opposing electrode for the DRAM capacitor cell. Gas phase etches involving only fluorine (either remote or local) do not possess the selectivity needed to remove the mold oxide and leave other portions of the patterned substrate essentially undisturbed. Remote NF₃/NH₃ etches provide some of the desired selectivity, especially silicon oxide to silicon selectivity. However, these remote etches produce solid residue which must be removed via sublimation. Architectures like the one cylindrical storage node (OCS) DRAM have been found to deform as a result of the production of the solid residue. The gas phase etches described herein do not produce solid residue, yet still offer high selectivity like remote NF₃/NH₃ etches.

Without wishing to bind the coverage of the claims to theoretical mechanisms which may or may not be entirely correct, some discussion of possible mechanisms may prove beneficial. Radical-fluorine precursors are produced by delivering a fluorine-containing precursor into the remote plasma region. Applicants suppose that a concentration of fluorine ions and atoms is produced and delivered into the substrate processing region. Water vapor (H₂O) may react with the fluorine to produce less reactive species such as HF₂ ⁻ which still readily remove silicon oxide but do not readily remove silicon and silicon nitride from the patterned substrate surface. The selectivity combined with the lack of solid byproducts, make these etch processes well suited for removing molds and other silicon oxide support structures from delicate non-silicon oxide materials while inducing little deformation in the remaining delicate structures.

The conducting column (titanium nitride in the example) loses physical support as the mold silicon oxide is removed from its perimeter. In some instances, the gas phase etch presented herein may also result in some tolerable bowing (e.g. leaning) of the conducting columns, but would generally be within a few degrees of vertical. Applicants have further found that introducing some alcohol into the substrate processing region can reduce the forces which result in deformation of the conducting column. In embodiments, the alcohol includes one or more of methanol, ethanol and isopropyl alcohol. The alcohol is introduced in a manner similar to the water vapor, i.e. the alcohol does not pass through a remote plasma before entering the substrate processing region. In embodiments, the alcohol is combined with the water vapor and flowed into the substrate processing region together.

FIGS. 2A-2B are charts of etch rates of remotely-excited-fluorine and water vapor etches of silicon oxide conducted at different temperatures and pressures according to disclosed embodiments. The data show a gradual reduction in etch rate as the temperature of the substrate is increased from 0° C. up through 15° C. In embodiments, the temperature of the substrate during remotely-excited-fluorine and water vapor etches described herein is less than or about 10° C., less than or about 5° C. or less than or about 0° C. in different embodiments. The data further show an increase in etch rate as a function of process pressure. In FIG. 2B, the diamonds represent etched amounts of silicon oxide for a process pressure near 10 Torr whereas the squares represent measurements with a process pressure of about 5 Torr. The pressure within the substrate processing region is below or about 50 Torr and above or about 5 Torr or 10 Torr in disclosed embodiments. The upper limit can be combined with either lower limit to form additional embodiments of the invention.

FIG. 3 is a chart of silicon oxide selectivity compared to silicon nitride and silicon for silicon oxide selective etch processes according to disclosed embodiments. Selectivities are graphed for low substrate temperature (0° C., left) and “high” substrate temperature (10° C., right). The etch selectivity of silicon oxide relative to silicon nitride in both cases is greater than or about 40:1 and the selectivity of silicon oxide relative to silicon is greater than or about 100:1.

Additional water vapor and remotely-excited-fluorine etch process parameters are disclosed in the course of describing an exemplary processing chamber and system.

Exemplary Processing System

Processing chambers that may implement embodiments of the present invention may be included within processing platforms such as the CENTURA® and PRODUCER® systems, available from Applied Materials, Inc. of Santa Clara, Calif. Examples of substrate processing chambers that can be used with exemplary methods of the invention may include those shown and described in co-assigned U.S. Provisional Patent App. No. 60/803,499 to Lubomirsky et al, filed May 30, 2006, and titled “PROCESS CHAMBER FOR DIELECTRIC GAPFILL,” the entire contents of which is herein incorporated by reference for all purposes. Additional exemplary systems may include those shown and described in U.S. Pat. Nos. 6,387,207 and 6,830,624, which are also incorporated herein by reference for all purposes.

FIG. 4A is a substrate processing chamber 400 according to disclosed embodiments. A remote plasma system (RPS 410) may process the fluorine-containing precursor which then travels through a gas inlet assembly 411. Two distinct gas supply channels are visible within the gas inlet assembly 411. A first channel 412 carries a gas that passes through the remote plasma system RPS 410, while a second channel 413 bypasses the RPS 410. Either channel may be used for the fluorine-containing precursor, in embodiments. On the other hand, the first channel 402 may be used for the process gas and the second channel 413 may be used for a treatment gas. The lid 421 (e.g. a conducting top portion) and a perforated partition (showerhead 453) are shown with an insulating ring 424 in between, which allows an AC potential to be applied to the lid 421 relative to showerhead 453. The AC potential strikes a plasma in chamber plasma region 420. The process gas may travel through first channel 412 into chamber plasma region 420 and may be excited by a plasma in chamber plasma region 420 alone or in combination with RPS 410. If the process gas (the fluorine-containing precursor) flows through second channel 413, then only the chamber plasma region 420 is used for excitation. The combination of chamber plasma region 420 and/or RPS 410 may be referred to as a remote plasma system herein. The perforated partition (also referred to as a showerhead) 453 separates chamber plasma region 420 from a substrate processing region 470 beneath showerhead 453. Showerhead 453 allows a plasma present in chamber plasma region 420 to avoid directly exciting gases in substrate processing region 470, while still allowing excited species to travel from chamber plasma region 420 into substrate processing region 470.

Showerhead 453 is positioned between chamber plasma region 420 and substrate processing region 470 and allows plasma effluents (excited derivatives of precursors or other gases) created within RPS 410 and/or chamber plasma region 420 to pass through a plurality of through-holes 456 that traverse the thickness of the plate. The showerhead 453 also has one or more hollow volumes 451 which can be filled with a precursor in the form of a vapor or gas (such as a silicon-containing precursor) and pass through small holes 455 into substrate processing region 470 but not directly into chamber plasma region 420. Showerhead 453 is thicker than the length of the smallest diameter 450 of the through-holes 456 in this disclosed embodiment. In order to maintain a significant concentration of excited species penetrating from chamber plasma region 420 to substrate processing region 470, the length 426 of the smallest diameter 450 of the through-holes may be restricted by forming larger diameter portions of through-holes 456 part way through the showerhead 453. The length of the smallest diameter 450 of the through-holes 456 may be the same order of magnitude as the smallest diameter of the through-holes 456 or less in disclosed embodiments.

In the embodiment shown, showerhead 453 may distribute (via through-holes 456) process gases which contain oxygen, hydrogen and/or nitrogen and/or plasma effluents of such process gases upon excitation by a plasma in chamber plasma region 420. In embodiments, the process gas introduced into the RPS 410 and/or chamber plasma region 420 through first channel 412 may contain fluorine (e.g. CF₄, NF₃ or XeF₂). The process gas may also include a carrier gas such as helium, argon, nitrogen (N₂), etc. Plasma effluents may include ionized or neutral derivatives of the process gas and may also be referred to herein as a radical-fluorine precursor referring to the atomic constituent of the process gas introduced.

In embodiments, the number of through-holes 456 may be between about 60 and about 2000. Through-holes 456 may have a variety of shapes but are most easily made round. The smallest diameter 450 of through-holes 456 may be between about 0.5 mm and about 20 mm or between about 1 mm and about 6 mm in disclosed embodiments. There is also latitude in choosing the cross-sectional shape of through-holes, which may be made conical, cylindrical or a combination of the two shapes. The number of small holes 455 used to introduce a gas into substrate processing region 470 may be between about 100 and about 5000 or between about 500 and about 2000 in different embodiments. The diameter of the small holes 455 may be between about 0.1 mm and about 2 mm.

FIG. 4B is a bottom view of a showerhead 453 for use with a processing chamber according to disclosed embodiments. Showerhead 453 corresponds with the showerhead shown in FIG. 4A. Through-holes 456 are depicted with a larger inner-diameter (ID) on the bottom of showerhead 453 and a smaller ID at the top. Small holes 455 are distributed substantially evenly over the surface of the showerhead, even amongst the through-holes 456 which helps to provide more even mixing than other embodiments described herein.

An exemplary patterned substrate may be supported by a pedestal (not shown) within substrate processing region 470 when fluorine-containing plasma effluents arriving through through-holes 456 in showerhead 453 combine with moisture arriving through the small holes 455 originating from hollow volumes 451. Though substrate processing region 470 may be equipped to support a plasma for other processes such as curing, no plasma is present during the etching of patterned substrate, in embodiments of the invention.

A plasma may be ignited either in chamber plasma region 420 above showerhead 453 or substrate processing region 470 below showerhead 453. A plasma is present in chamber plasma region 420 to produce the radical-fluorine precursors from an inflow of the fluorine-containing precursor. An AC voltage typically in the radio frequency (RF) range is applied between the conductive top portion 421 of the processing chamber and showerhead 453 to ignite a plasma in chamber plasma region 420 during deposition. An RF power supply generates a high RF frequency of 13.56 MHz but may also generate other frequencies alone or in combination with the 13.56 MHz frequency.

The top plasma may be left at low or no power when the bottom plasma in the substrate processing region 470 is turned on to either cure a film or clean the interior surfaces bordering substrate processing region 470. A plasma in substrate processing region 470 is ignited by applying an AC voltage between showerhead 453 and the pedestal or bottom of the chamber. A cleaning gas may be introduced into substrate processing region 470 while the plasma is present.

The pedestal may have a heat exchange channel through which a heat exchange fluid flows to control the temperature of the substrate. This configuration allows the substrate temperature to be cooled or heated to maintain relatively low temperatures (from room temperature through about 120° C.). The heat exchange fluid may comprise ethylene glycol and water. The wafer support platter of the pedestal (preferably aluminum, ceramic, or a combination thereof) may also be resistively heated in order to achieve relatively high temperatures (from about 120° C. through about 1100° C.) using an embedded single-loop embedded heater element configured to make two full turns in the form of parallel concentric circles. An outer portion of the heater element may run adjacent to a perimeter of the support platter, while an inner portion runs on the path of a concentric circle having a smaller radius. The wiring to the heater element passes through the stem of the pedestal.

The substrate processing system is controlled by a system controller. In an exemplary embodiment, the system controller includes a hard disk drive, a floppy disk drive and a processor. The processor contains a single-board computer (SBC), analog and digital input/output boards, interface boards and stepper motor controller boards. Various parts of CVD system conform to the Versa Modular European (VME) standard which defines board, card cage, and connector dimensions and types. The VME standard also defines the bus structure as having a 16-bit data bus and a 24-bit address bus.

The system controller controls all of the activities of the etching chamber. The system controller executes system control software, which is a computer program stored in a computer-readable medium. Preferably, the medium is a hard disk drive, but the medium may also be other kinds of memory. The computer program includes sets of instructions that dictate the timing, mixture of gases, chamber pressure, chamber temperature, RF power levels, susceptor position, and other parameters of a particular process. Other computer programs stored on other memory devices including, for example, a floppy disk or other another appropriate drive, may also be used to instruct the system controller.

A process for depositing a film stack on a substrate or a process for cleaning a chamber can be implemented using a computer program product that is executed by the system controller. The computer program code can be written in any conventional computer readable programming language: for example, 68000 assembly language, C, C++, Pascal, Fortran or others. Suitable program code is entered into a single file, or multiple files, using a conventional text editor, and stored or embodied in a computer usable medium, such as a memory system of the computer. If the entered code text is in a high level language, the code is compiled, and the resultant compiler code is then linked with an object code of precompiled Microsoft Windows® library routines. To execute the linked, compiled object code the system user invokes the object code, causing the computer system to load the code in memory. The CPU then reads and executes the code to perform the tasks identified in the program.

The interface between a user and the controller is via a flat-panel touch-sensitive monitor. In the preferred embodiment two monitors are used, one mounted in the clean room wall for the operators and the other behind the wall for the service technicians. The two monitors may simultaneously display the same information, in which case only one accepts input at a time. To select a particular screen or function, the operator touches a designated area of the touch-sensitive monitor. The touched area changes its highlighted color, or a new menu or screen is displayed, confirming communication between the operator and the touch-sensitive monitor. Other devices, such as a keyboard, mouse, or other pointing or communication device, may be used instead of or in addition to the touch-sensitive monitor to allow the user to communicate with the system controller.

The chamber plasma region or a region in an RPS may be referred to as a remote plasma region. In embodiments, the radical precursor (e.g. a radical-fluorine precursor) is created in the remote plasma region and travels into the substrate processing region to combine with the water vapor. In embodiments, the water vapor is excited only by the radical-fluorine precursor. Plasma power may essentially be applied only to the remote plasma region, in embodiments, to ensure that the radical-fluorine precursor provides the dominant excitation to the water vapor.

In embodiments employing a chamber plasma region, the excited plasma effluents are generated in a section of the substrate processing region partitioned from a deposition region. The deposition region, also known herein as the substrate processing region, is where the plasma effluents mix and react with the water vapor to etch the patterned substrate (e.g., a semiconductor wafer). The excited plasma effluents may also be accompanied by inert gases (in the exemplary case, argon). The water vapor does not pass through a plasma before entering the substrate plasma region, in embodiments. The substrate processing region may be described herein as “plasma-free” during the etch of the patterned substrate. “Plasma-free” does not necessarily mean the region is devoid of plasma. Ionized species and free electrons created within the plasma region do travel through pores (apertures) in the partition (showerhead) but the water vapor is not substantially excited by the plasma power applied to the plasma region. The borders of the plasma in the chamber plasma region are hard to define and may encroach upon the substrate processing region through the apertures in the showerhead. In the case of an inductively-coupled plasma, a small amount of ionization may be effected within the substrate processing region directly. Furthermore, a low intensity plasma may be created in the substrate processing region without eliminating desirable features of the forming film. All causes for a plasma having much lower intensity ion density than the chamber plasma region (or a remote plasma region, for that matter) during the creation of the excited plasma effluents do not deviate from the scope of “plasma-free” as used herein.

Nitrogen trifluoride (or another fluorine-containing precursor) may be flowed into chamber plasma region 420 at rates between about 25 sccm and about 200 sccm, between about 50 sccm and about 150 sccm or between about 75 sccm and about 125 sccm in different embodiments. Water vapor may be flowed into substrate processing region 470 at rates between about 25 sccm and about 200 sccm, between about 50 sccm and about 150 sccm or between about 75 sccm and about 125 sccm in different embodiments. Ethanol (or another alcohol) may be flowed into substrate processing region 470 at rates below or about 100 sccm, below or about 50 sccm or below or about 25 sccm in different embodiments.

Combined flow rates of water vapor, fluorine-containing precursor and alcohol into the chamber may account for 0.05% to about 20% by volume of the overall gas mixture: the remainder being carrier gases. The fluorine-containing precursor is flowed into the remote plasma region but the plasma effluents has the same volumetric flow ratio, in embodiments. In the case of the fluorine-containing precursor, a purge or carrier gas may be first initiated into the remote plasma region before those of the fluorine-containing gas to stabilize the pressure within the remote plasma region.

Plasma power can be a variety of frequencies or a combination of multiple frequencies. In the exemplary processing system the plasma is provided by RF power delivered to lid 421 relative to showerhead 453. The RF power may be between about 100 W and about 2000 W, between about 200 W and about 1500 W or between about 500 W and about 1000 W in different embodiments. The RF frequency applied in the exemplary processing system may be low RF frequencies less than about 200 kHz, high RF frequencies between about 10 MHz and about 15 MHz or microwave frequencies greater than or about 1 GHz in different embodiments.

Substrate processing region 470 can be maintained at a variety of pressures during the flow of water vapor, any carrier gases and plasma effluents into substrate processing region 470. The pressure may be maintained between about 500 mTorr and about 30 Torr, between about 1 Torr and about 20 Torr or between about 5 Torr and about 15 Torr in different embodiments.

In one or more embodiments, the substrate processing chamber 400 can be integrated into a variety of multi-processing platforms, including the Producer™ GT, Centura™ AP and Endura™ platforms available from Applied Materials, Inc. located in Santa Clara, Calif. Such a processing platform is capable of performing several processing operations without breaking vacuum. Processing chambers that may implement embodiments of the present invention may include dielectric etch chambers or a variety of chemical vapor deposition chambers, among other types of chambers.

Embodiments of the deposition systems may be incorporated into larger fabrication systems for producing integrated circuit chips. FIG. 5 shows one such system 500 of deposition, baking and curing chambers according to disclosed embodiments. In the figure, a pair of FOUPs (front opening unified pods) 502 supply substrate substrates (e.g., 300 mm diameter wafers) that are received by robotic arms 504 and placed into a low pressure holding area 506 before being placed into one of the substrate processing chambers 508 a-f. A second robotic arm 510 may be used to transport the substrate wafers from the holding area 506 to the substrate processing chambers 508 a-f and back. Each substrate processing chamber 508 a-f, can be outfitted to perform a number of substrate processing operations including the dry etch processes described herein in addition to cyclical layer deposition (CLD), atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD), etch, pre-clean, degas, orientation and other substrate processes.

The substrate processing chambers 508 a-f may include one or more system components for depositing, annealing, curing and/or etching a flowable dielectric film on the substrate wafer. In one configuration, two pairs of the processing chamber (e.g., 508 c-d and 508 e-f) may be used to deposit dielectric material on the substrate, and the third pair of processing chambers (e.g., 508 a-b) may be used to etch the deposited dielectric. In another configuration, all three pairs of chambers (e.g., 508 a-f) may be configured to etch a dielectric film on the substrate. Any one or more of the processes described may be carried out on chamber(s) separated from the fabrication system shown in different embodiments.

System controller 557 is used to control motors, valves, flow controllers, power supplies and other functions required to carry out process recipes described herein. A gas handling system 555 may also be controlled by system controller 557 to introduce gases to one or all of the substrate processing chambers 508 a-f. System controller 557 may rely on feedback from optical sensors to determine and adjust the position of movable mechanical assemblies in gas handling system 555 and/or in substrate processing chambers 508 a-f. Mechanical assemblies may include the robot, throttle valves and susceptors which are moved by motors under the control of system controller 557.

In an exemplary embodiment, system controller 557 includes a hard disk drive (memory), USB ports, a floppy disk drive and a processor. System controller 557 includes analog and digital input/output hoards, interface boards and stepper motor controller boards. Various parts of multi-chamber processing system 500 which contains processing chamber 400 are controlled by system controller 557. The system controller executes system control software in the form of a computer program stored on computer-readable medium such as a hard disk, a floppy disk or a flash memory thumb drive. Other types of memory can also be used. The computer program includes sets of instructions that dictate the timing, mixture of gases, chamber pressure, chamber temperature, RF power levels, susceptor position, and other parameters of a particular process.

A process for etching, depositing or otherwise processing a film on a substrate or a process for cleaning chamber can be implemented using a computer program product that is executed by the controller. The computer program code can be written in any conventional computer readable programming language: for example, 68000 assembly language, C, C++, Pascal, Fortran or others. Suitable program code is entered into a single file, or multiple files, using a conventional text editor, and stored or embodied in a computer usable medium, such as a memory system of the computer. If the entered code text is in a high level language, the code is compiled, and the resultant compiler code is then linked with an object code of precompiled Microsoft Windows® library routines. To execute the linked, compiled object code the system user invokes the object code, causing the computer system to load the code in memory. The CPU then reads and executes the code to perform the tasks identified in the program.

The interface between a user and the controller may be via a touch-sensitive monitor and may also include a mouse and keyboard. In one embodiment two monitors are used, one mounted in the clean room wall for the operators and the other behind the wall for the service technicians. The two monitors may simultaneously display the same information, in which case only one is configured to accept input at a time. To select a particular screen or function, the operator touches a designated area on the display screen with a finger or the mouse. The touched area changes its highlighted color, or a new menu or screen is displayed, confirming the operator's selection.

As used herein “substrate” may be a support substrate with or without layers formed thereon. The patterned substrate may be an insulator or a semiconductor of a variety of doping concentrations and profiles and may, for example, be a semiconductor substrate of the type used in the manufacture of integrated circuits. Exposed “silicon oxide” of the patterned substrate is predominantly SiO₂ but may include concentrations of other elemental constituents such as nitrogen, hydrogen, carbon and the like. In some embodiments, silicon oxide films etched using the methods disclosed herein consist essentially of silicon and oxygen. The term “precursor” is used to refer to any process gas which takes part in a reaction to either remove material from or deposit material onto a surface. “Plasma effluents” describe gas exiting from the chamber plasma region and entering the substrate processing region. Plasma effluents are in an “excited state” wherein at least some of the gas molecules are in vibrationally-excited, dissociated and/or ionized states. A “radical precursor” is used to describe plasma effluents (a gas in an excited state which is exiting a plasma) which participate in a reaction to either remove material from or deposit material on a surface. A “radical-fluorine precursor” is a radical precursor which contains fluorine but may contain other elemental constituents. The phrase “inert gas” refers to any gas which does not form chemical bonds when etching or being incorporated into a film. Exemplary inert gases include noble gases but may include other gases so long as no chemical bonds are formed when (typically) trace amounts are trapped in a film.

The terms “gap” and “trench” are used throughout with no implication that the etched geometry has a large horizontal aspect ratio. Viewed from above the surface, trenches may appear circular, oval, polygonal, rectangular, or a variety of other shapes. A trench may be in the shape of a moat around an island of material (e.g. a substantially cylindrical TiN pillar). The term “via” is used to refer to a low aspect ratio trench (as viewed from above) which may or may not be filled with metal to form a vertical electrical connection. As used herein, a conformal etch process refers to a generally uniform removal of material on a surface in the same shape as the surface, i.e., the surface of the etched layer and the pre-etch surface are generally parallel. A person having ordinary skill in the art will recognize that the etched interface likely cannot be 100% conformal and thus the term “generally” allows for acceptable tolerances.

Having disclosed several embodiments, it will be recognized by those of skill in the art that various modifications, alternative constructions, and equivalents may be used without departing from the spirit of the disclosed embodiments. Additionally, a number of well known processes and elements have not been described in order to avoid unnecessarily obscuring the present invention. Accordingly, the above description should not be taken as limiting the scope of the invention.

Where a range of values is provided, it is understood that each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limits of that range is also specifically disclosed. Each smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in that stated range is encompassed. The upper and lower limits of these smaller ranges may independently be included or excluded in the range, and each range where either, neither or both limits are included in the smaller ranges is also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included.

As used herein and in the appended claims, the singular forms “a”, “an”, and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a process” includes a plurality of such processes and reference to “the dielectric material” includes reference to one or more dielectric materials and equivalents thereof known to those skilled in the art, and so forth.

Also, the words “comprise,” “comprising,” “include,” “including,” and “includes” when used in this specification and in the following claims are intended to specify the presence of stated features, integers, components, or steps, but they do not preclude the presence or addition of one or more other features, integers, components, steps, acts, or groups. 

What is claimed is:
 1. A method of etching a patterned substrate in a substrate processing region of a substrate processing chamber, wherein the patterned substrate has an exposed silicon oxide region, the method comprising: flowing a fluorine-containing precursor into a remote plasma region fluidly coupled to the substrate processing region through pores in a showerhead while forming a remote plasma in the remote plasma region to produce plasma effluents; flowing water vapor into the substrate processing region without first passing the water vapor through the remote plasma region, wherein the substrate processing region is plasma-free; and etching the exposed silicon oxide region by flowing the plasma effluents through the pores in the showerhead into the substrate processing region, wherein the plasma effluents mix and react with the water vapor and the water vapor is only excited by interaction with the plasma effluents.
 2. The method of claim 1 wherein the exposed silicon oxide region surrounds an electrically conducting column comprising electrically conducting material prior to the operation of etching the exposed silicon oxide region.
 3. The method of claim 2 wherein the electrically conducting column does not substantially bow out as a result of the removal of the exposed silicon oxide region after the operation of etching the exposed silicon oxide region.
 4. The method of claim 2 wherein the electrically conducting material comprises titanium.
 5. The method of claim 4 wherein the electrically conducting material comprises titanium nitride.
 6. The method of claim 2 wherein the electrically conducting column is cylindrically shaped.
 7. The method of claim 6 wherein a diameter of the electrically conducting column is less than or about 70 nm.
 8. The method of claim 1 wherein the operation of flowing water vapor into the substrate processing region further comprises flowing an alcohol into the substrate processing region, also without first passing the alcohol through the remote plasma region.
 9. The method of claim 1 wherein the substrate processing region is plasma-free.
 10. The method of claim 1 wherein the water vapor is not excited by any remote plasma formed outside the substrate processing region.
 11. The method of claim 8 wherein the alcohol is not excited by any remote plasma formed outside the substrate processing region.
 12. The method of claim 8 wherein the alcohol is selected from the group consisting of methanol, ethanol and isopropyl alcohol.
 13. The method of claim 1 wherein the fluorine-containing precursor comprises a precursor selected from the group consisting of atomic fluorine, diatomic fluorine, nitrogen trifluoride, carbon tetrafluoride, hydrogen fluoride and xenon difluoride.
 14. The method of claim 1 wherein the fluorine-containing precursor and the plasma effluents are essentially devoid of hydrogen. 